Enhanced cellulose nanofibrils (cnf)

ABSTRACT

An enhanced cellulose nanofibrils (CNF) (or enhanced CNF binder), methods of making the enhanced CNF binder, methods of making wet-laid, dry-laid, or molded articles with the enhanced CNF binder by incorporating the enhanced CNF with the furnish in the wet-end of a paper-making process, methods of coating cellulose-based materials, intermediate formed fiber articles, and/or molded articles with the enhanced CNF binder, and cellulose-based articles obtained by all of these methods, wherein the enhanced CNF includes a saccharide fatty acid ester-, glyceride-, fatty acid salt-, natural wax- and/or cellulose crosslinker-(SGF) blend bound to the CNF.

FIELD OF THE DISCLOSURE

The present disclosure relates to an enhanced cellulose nanofibrils(CNF) (or enhanced CNF binder), methods of making the enhanced CNFbinder, methods of making wet-laid, dry-laid, or molded articles withthe enhanced CNF binder by incorporating the enhanced CNF with thefurnish in the wet-end of a paper-making process, methods of coatingcellulose-based materials, intermediate formed fiber articles, and/ormolded articles with the enhanced CNF binder, and cellulose-basedarticles obtained by all of these methods, wherein the enhanced CNFincludes a saccharide fatty acid ester-, glyceride-, fatty acid salt-,natural wax- and/or cellulose crosslinker- (SGF) blend bound to the CNF.

BACKGROUND OF THE DISCLOSURE

Cellulosic materials have a wide range of applications in industry asbulking agents, absorbents, and printing components. Their employment ispreferred to that of other sources of material for their high thermalstability, good oxygen barrier function, and chemical/mechanicalresilience (see, e.g., Aulin et al., Cellulose (2010) 17:559-574;incorporated herein by reference in its entirety). Of great relevance isalso the fact that these materials are fully biodegradable oncedispersed in the environment, and that they are totally nontoxic.Cellulose and derivatives thereof are the material of choice forenvironmentally friendly solutions in applications such as packaging forfoodstuff and disposable goods.

The many advantages of cellulose are nonetheless countered by thehydrophilicity/lipophilicity of the cellulose material, which shows ahigh affinity for water/fats and are easily hydrated (see, e.g., Aulinet al., Langmuir (2009) 25(13):7675-7685; incorporated herein byreference in its entirety). While this is a benefit for applicationssuch as absorbents and tissues, it becomes an issue when the safepackaging of watery/lipid containing materials (e.g., foodstuffs) isrequired. Long term storage of food, especially ready-made meals whichcontain a significant amount of water and/or fat, is made problematic incellulose trays, for example, as they would first become soggy and thenultimately fail. Further, multiple coatings may be required to offsetlow efficiency of maintaining sufficient coating on the cellulosicsurface due to the high relative porosity of the material, resulting inincreased costs.

This problem is usually addressed in the industry by coating thecellulose fiber with some kind of hydrophobic organicmaterial/fluorocarbons (e.g., per- and polyfluoroalkyl substances(PFAS)), wax, synthetic polymers (e.g., polyethylene), silicones, whichwould physically shield the underlying hydrophilic cellulose from thewater/lipids in the contents, including the prevention of wicking in thefiber interstices, grease flowing into creases, or allowing the releaseof attached materials. For example, materials such as PVC/PEI/PE areroutinely used for this purpose and are physically attached (i.e., spraycoated or extruded) on the surfaces to be treated.

Industry has utilized compounds based on fluorocarbon chemistry for manyyears to produce articles having improved resistance to penetration byoil and grease, due to the ability of fluorocarbons to lower the surfaceenergy of the articles. One emerging issue with the use ofperfluorinated hydrocarbons is that they are remarkably persistent inthe environment. The EPA and FDA have recently begun a review of thesource, environmental fate, and toxicity of these compounds. A recentstudy reported a very high (>90%) rate of occurrence of perfluorooctanesulfonate in blood samples taken from school children. The expense andpotential environmental liability of these compounds has drivenmanufacturers to seek alternative means of producing articles havingresistance to penetration by oil and grease.

While lowering the surface energy improves the penetration resistance ofthe articles, lowering the surface energy also has some disadvantages.For example, a textile fabric treated with a fluorocarbon will exhibitgood stain resistance; however, once soiled, the ability of cleaningcompositions to penetrate and hence release the soil from the fabric maybe affected, which can result in permanently soiled fabrics of reduceduseful life. Another example is a greaseproof paper which is to besubsequently printed and/or coated with an adhesive. In this case therequisite grease resistance is attained by treatment with thefluorocarbon, but the low surface energy of the paper may cause problemsrelated to printing ink or adhesive receptivity, including scuffing,back trap mottle, poor adhesion, and register. If a greaseproof paper isto be used as a pressure sensitive label having an adhesive applied onone side, the low surface energy may reduce the strength of theadhesion. To improve their printability, coat-ability or adhesion, thelow surface energy articles can be treated by post forming processessuch as corona discharge, chemical treatment, flame treatment, or thelike. However, these processes increase the cost of producing thearticles and may have other disadvantages.

It would be desirable to design a “green,” bio-based coating which ishydrophobic, lipophobic and compostable, including a base paper/filmthat would allow for keeping coatings on the surface of said paper andpreventing wicking into the fiber interstices, or reducing sticking ofmaterials to the cellulosic surface, at reduced costs, withoutsacrificing biodegradability and/or recyclability.

Another problem is that conventional coatings for imparting hydrophobicand/or lipophobic barrier properties, including the fluorocarbon andpetrochemical coatings noted herein, is that they tend to perform poorlyat the folds, creases, and the like of the article coated with thematerial. Specifically, the article typically has inferior waterresistance and/or grease resistance at these locations. Such a “greasecreasing effect” may be defined as the sorption of grease in a paperstructure that is created by folding, pressing or crushing said paperstructure. A conventional solution to the grease creasing effect is toadd a latex, a polyvinyl alcohol, or similar resin to the coating toachieve improved coating coverage at these locations. However, with thisconventional solution, the water resistance and/or oil and greaseresistance of these locations may still be inferior to the flat portionsof the article; this conventional solution increases cost by theaddition of the resin component; and this conventional solution is notentirely bio-based, since the latex and polyvinyl alcohol may either besynthetic and/or not easily recyclable.

U.S. Patent Application Publication No. 2018/0066073 (hereinafter “the'073 publication”), which is incorporated herein by reference in itsentirety, discloses tunable methods of treating cellulosic materialswith a composition that provides increased barrier properties, such aswater resistance and/or oil and grease resistance (OGR), withoutsacrificing the biodegradability thereof. In particular, the '073application discloses methods of binding of saccharide fatty acid esters(“SFAE”) on cellulosic materials to provide treated materials thatdisplay higher water resistance, lipid resistance, barrier function, andother mechanical properties.

U.S. Provisional Patent Application Publication No. 63/022,097, filedMay 8, 2020, (hereinafter “the '097 application”), which is incorporatedherein by reference in its entirety, discloses tunable methods oftreating cellulosic materials with a composition that provides increasedbarrier properties, such as water resistance and/or OGR resistance,without sacrificing the biodegradability thereof. In particular, the'097 application discloses methods of binding blends of glyceridesand/or fatty acid salts. The '097 application discloses that the barrierformulation including the blends of glycerides and/or fatty acid saltscan additionally include SFAE for imparting the water and/or OGRresistance and/or for providing the function of an emulsifier.

PCT/US2020/014923 (hereinafter “the '923 application”), which isincorporated herein by reference in its entirety, discloses methods oftreating fibrous cellulosic materials with sucrose fatty acid estercontaining particles (carrier systems) that allow for modifications ofsurfaces, including making such surfaces water resistance and/oroil/grease resistance. The methods as disclosed provide combining atleast one SFAE with a polymer (e.g., latexes) to form micellularparticles and applying such particles to substrates including fibrouscellulose-based materials (e.g., pulp) to form, inter alia, moldedproducts. Compositions comprising combinations of SFAE, a latex andoptionally a mineral or other additives are also disclosed.

U.S. Ser. No. 16/568,953 (hereinafter “the '953 application”), which isincorporated herein by reference in its entirety, discloses tunablemethods of treating cellulosic materials with a barrier coatingcomprising a prolamin and at least one polyol fatty acid ester thatprovides increased oil and/or grease resistance to such materialswithout sacrificing the biodegradability thereof. The methods asdisclosed provide for adhering of the barrier coating on articlesincluding articles comprising cellulosic materials and articles made bysuch methods. The materials thus treated display higher lipophobicityand may be used in any application where such features are desired.

U.S Ser. No. 16/456,499 (hereinafter “the '499 application”), which isincorporated herein by reference in its entirety, discloses tunablemethods of treating cellulosic materials with a barrier coatingcomprising at least two polyol and/or saccharide fatty acid ester thatprovides increased water, oil and grease resistance to such materialswithout sacrificing the biodegradability thereof. The methods asdisclosed provide for adhering of the barrier coating on articlesincluding articles comprising cellulosic materials and articles made bysuch methods. The materials thus treated display higher hydrophobicityand lipophobicity and may be used in any application where such featuresare desired.

U.S. Ser. No. 16/456,433 (hereinafter “the '433 application”), which isincorporated herein by reference in its entirety, discloses methods oftreating cellulosic materials with compositions that allow greaterretention of inorganic particles on cellulosic substrates. The methodsas disclosed provide combining SFAE with such inorganic particles andapplying such combinations on cellulosic materials to eliminate orreduce the use of retention aids or binders for filler in the papermaking process. Compositions comprising such combinations of SFAE andinorganic particles are also disclosed.

The use of a binder obtained from a natural source has also become ofincreasing importance for providing a “green,” biobased product.

Nanocellulose is a term referring to nano-structured cellulose, whichmay be cellulose nanocrystals (CNC or NCC), cellulose nanofibrils (CNF)(which are also referred to in the art as cellulose nanofibers andnanofibrilated cellulose), or bacterial nanocellulose.

CNF is a material composed of nanosized cellulose fibrils typicallyhaving a high aspect ratio (length to width ratio). CNF is typicallyobtained from woodpulp or another natural source of cellulose fibers,typically by a process that includes subjecting the pulp/fibers tomechanical shear forces.

CNF has been used as a binder in the papermaking process. In thisregard, the inventors determined that the use of CNF as an additive onthe wet-end and in coating applications can provide improved OGR.However, the use of CNF presents certain problems. One problem is that,when the CNF is used as a wet-end addition to the papermaking furnish,the CNF tends to slow the drainage rate (or dewatering) of the fiber matfrom the slurry. This is detrimental, for example, because the waterremoval rate dictates the production speed of the cellulose-basedproduct. Another problem is that the CNF tends to agglomerate when usedas an additive as a slurry or spray, which can negatively affect itsefficiency and/or its functional properties.

Based on the summary above, there is still a need for “green,” bio-basedcoatings for cellulose-based materials that provide improved waterand/or OGR resistance, and “green” cellulose-based molded articleshaving improved water and/or OGR resistance.

SUMMARY OF THE DISCLOSURE

The present disclosure provides methods that address one or more of thelimitations and/or concerns in the conventional art discussed aboveand/or provide one or more improvements thereon. However, the presentdisclosure is not required to address any of the limitations and/orconcerns.

In one embodiment, the disclosure is directed to an enhanced cellulosenanofibril binder, which includes: cellulose nanofibrils (CNF); and anSGF blend bound to the CNF, wherein the SGF blend comprises one or moreselected from the group consisting saccharide fatty acid esters (SFAE),glycerides, fatty acid salts (“FAS”), natural waxes, and cellulosecrosslinkers.

As used herein, the term “SGF blend” means one or more saccharide fattyacid esters (SFAE), and/or one or more glycerides), and/or one or morefatty acid salts (FAS), and/or one or more natural waxes, and/or one ormore cellulose crosslinkers. In some embodiments, the SGF blend used inthe present disclosure does not include a SFAE; in some embodiments theSGF blend does not include a glyceride; in some embodiments the SGFblend does not include a FAS; in some embodiments the SGF blend does notinclude the natural waxes; and in some embodiments the SGF blend doesnot include the cellulose crosslinkers. In some embodiments, the SGFblend consists essentially of the SFAE, glycerides, and/or FAS. In someembodiments, the SGF blend consists of the SFAE, glycerides, and/or FAS.

The enhanced cellulose nanofibril binder (or enhanced CNF) according tothe present disclosure can provide certain benefits. For example, whenused in the furnish on the wet-end of the papermaking process, theenhanced CNF maintains or increases the drainage rate of the fiber matfrom the slurry. Also, the enhanced CNF does not suffer the same problemof agglomeration as conventional CNF.

In one aspect of the present disclosure, the enhanced cellulosenanofibril binder consists essentially of the CNF and the SGF blend.

In another aspect of the enhanced cellulose nanofibril binder, a weightratio of the CNF to the SGF blend is about 1:99 to about 99:1, or about5:95 to about 95:5, or about 10:90 to about 90:10, or about 15:85 toabout 85:15, or about 20:80 to about 80:20, or about 25:75 to about75:25, or about 30:70 to about 70:30, or about 35:65 to about 65:35, orabout 40:60 to about 60:40, or about 45:55 to about 55:45, or about50:50.

In one embodiment, the enhanced cellulose nanofibril binder is obtainedby a method that includes: obtaining an aqueous mixture of cellulosenanofibrils (CNF); obtaining an aqueous SGF blend; and mixing theaqueous mixture of CNF with the aqueous SGF blend to obtain a CNF/SGFmixture. The mixing of the CNF with the SGF blend (and therebycontacting the CNF with the SGF blend) can be sufficient to bind the SGFblend to the CNF. Alternatively, the SGF blend can be bound to the CNFby exposing the CNF/SGF mixture to heat, radiation, a catalyst, or acombination thereof for a sufficient time. The method may furtherinclude a step of reducing the water content of the CNF/SGF mixture,such as by draining the water.

In one embodiment, the enhanced cellulose nanofibril binder according tothe present disclosure is obtained by a method that includes: obtainingan aqueous mixture of cellulose pulp (e.g., woodpulp); obtaining anaqueous SGF blend; mixing the aqueous mixture of cellulose pulp with theaqueous SGF blend to obtain a cellulose/SGF mixture; and subjecting thecellulose/SGF mixture to mechanical shear forces to obtain the enhancedcellulose nanofibril binder.

In one aspect, the method of obtaining the enhanced CNF may furtherinclude a step of reducing the water content of cellulose/SGF mixture,such as by draining the water.

In one aspect, the method of obtaining the enhanced CNF may furtherinclude subjecting the cellulose pulp to a pre-treatment prior toobtaining the cellulose/SGF mixture and/or prior to subjecting thecellulose/SGF mixture to the mechanical shear force.

In one aspect, the pre-treatment may include lower the pH of the aqueousmixture of cellulose pulp by adding an acid.

In one embodiment, the present disclosure provides a barrier formulationthat includes the enhanced CNF according to the present disclosure. Thecomposition of the barrier formulation can be chosen to tuneablyderivative a cellulose-based material by a method known in the art, suchas in the '073 publication or '097 application.

In one embodiment, the present disclosure provides a method of making acellulose-based article, the method including: adding the enhancedcellulose nanofibril binder according to the present disclosure to anaqueous papermaking furnish; and draining the water from the furnish toobtain a fibrous web.

In one aspect, the method further includes molding the fibrous web intoa molded article having a three-dimensional shape.

In one embodiment, a method for imparting a barrier property to acellulose-based material is provided, the method including contactingthe cellulose-based material with an aqueous barrier formulation forimparting the barrier property, the barrier formulation including theenhanced cellulose nanofibril binder according to the presentdisclosure; and binding the barrier formulation to a surface of thecellulose-based material to obtain a bound cellulose-based materialhaving die barrier property, wherein the barrier property is one or moreselected from the group consisting of water resistance, lipidresistance, and gas resistance.

In one embodiment, a barrier formulation is provided, the barrierformulation including the enhanced cellulose nanofibril binder accordingto the present disclosure a second SGF blend, the second SGF blendincluding one or more saccharide fatty acid esters (SFAE), one or moreglycerides, and/or one or more fatty acid salts; and water.

In one aspect, the second SGF blend of the barrier formulation can bechosen to tuneably derivative a cellulose-based material by a methodknown in the art, such as in the '073 publication or '097 application.

In one aspect, the barrier formulation of the present disclosure caninclude a pigment conventionally used in the papermaking industry.

In one embodiment, a method for imparting a barrier property to acellulose-based material, the method including: contacting thecellulose-based material with a barrier formulation for imparting thebarrier property, the barrier formulation including (a) cellulosenanofibrils (CNF), and (b) the SGF blend; and binding the barrierformulation to a surface of the cellulose-based material to obtain abound cellulose-based material having the barrier property, wherein thebarrier property is one or more selected from the group consisting ofwater resistance, lipid resistance, and gas resistance.

The method for imparting a barrier property according to the presentdisclosure can provide the same benefits noted above, which includesmaintaining or increasing the drainage rate when the method is appliedto a wet-end process, and preventing agglomeration of the CNF.

In one aspect, when a total weight of the barrier formulation used inthe method for imparting a barrier property according to the presentdisclosure is considered to be 100% by weight, the barrier formulationincludes about 4% by weight to about 96% by weight of the CNF, and about4% by weight to about 96% by weight of the SGF blend.

In one aspect, the cellulose-based material used in the method forimparting a barrier property according to the present disclosureincludes cellulose fiber, and the step of contacting includes forming anaqueous mixture of the barrier formulation and cellulose fiber.

In one aspect, the SGF blend can be present in the aqueous mixture ordispersion at a total concentration of at least 0.025% (wt/wt) of thetotal cellulose fiber present in the aqueous mixture.

In one aspect, the aqueous mixture includes one or more pigmentsconventionally used in the papermaking industry.

In one aspect, the aqueous mixture is in the form of a slurry having asolid content of about 0.1 to 10.0 wt. %, 0.1 to 6.0 wt. %, or about 0.1to 2.0 wt. %, or about 0.2 to 1.5 wt. %.

In one aspect, the method further includes reducing the water content ofthe aqueous mixture, such as by draining the water.

In another aspect, the step of contacting in the method for imparting abarrier property according to the present disclosure includes coatingthe surface of a cellulose-based substrate with the formulation by aprocess of immersion, spraying, painting, printing, or any combinationof any of these processes.

In one aspect, the SGF blend is present at a weight of at least about0.05 g/m² on the surface of the substrate.

The cellulose-based substrate is not particularly limited. In oneaspect, examples of the cellulose-based substrate include a surface ofan article selected from paper, paperboard, bacon board, insulatingmaterial, paper pulp, a carton for food storage, a compost bag, a bagfor food storage, release paper, a shipping bag, weed-block/barrierfabric or film, mulching film, plant pots, packing beads, bubble wrap,oil absorbent material, laminates, envelops, gift cards, credit cards,gloves, raincoats, OGR paper, a shopping bag, diapers, membranes, eatingutensil, a tea bag, a container for coffee or tea, a container forholding hot or cold beverages, a cup, a plate, a bottle for carbonatedliquid storage, a bottle for non-carbonated liquid storage, a lid, filmfor wrapping food, a garbage disposal container, a food handlingimplement, a fabric fibre, a water storage and conveying implement, astorage and conveying implement for alcoholic or non-alcoholicbeverages, an outer casing or screen for electronic goods, an internalor external piece of furniture, a curtain, upholstery, fabric, film, abox, a sheet, a tray, a pipe, a water conduit, clothing, a medicaldevice, pharmaceutical packaging, a contraceptive, camping equipment,cellulosic material that is molded, and combinations thereof.

In one aspect, the method for imparting a barrier property according tothe present disclosure provides a bound cellulose-based material thatexhibits a water contact angle of equal to or greater than 90°.

In one aspect, the method for imparting a barrier property according tothe present disclosure provides a bound cellulose-based material thatexhibits a TAPPI T 559 KIT test value of from 3 to 12.

In one aspect, the method for imparting a barrier property according tothe present disclosure provides a bound cellulose-based material thatexhibits a water contact angle of equal to or greater than 90° and/or aTAPPI T 559 KIT test value of from 3 to 12 in the absence of anysecondary hydrophobes.

In one embodiment, a method of making an enhanced cellulose nanofibrilbinder is provided, the method including: obtaining an aqueous mixtureof cellulose nanofibrils (CNF); obtaining an aqueous SGF blend; andmixing the aqueous mixture of CNF with the aqueous SGF blend to obtain aCNF/SGF mixture and allowing the SGF blend bind to the CNF.

In one aspect, the method of making the enhanced CNF further includesreducing the water content of the CNF/SGF mixture.

In one embodiment, a method of making an enhanced cellulose nanofibrilbinder is provided, the method including: obtaining an aqueous mixtureof cellulose pulp; obtaining an aqueous SGF blend; mixing the aqueousmixture of cellulose pulp with the aqueous SGF blend to obtain acellulose/SGF mixture; and subjecting the cellulose/SGF mixture tomechanical shear forces to obtain the enhanced cellulose nanofibrilbinder.

In one aspect, the method includes subjecting the cellulose pulp to apre-treatment prior to obtaining the cellulose/SGF mixture and/or priorto subjecting the cellulose/SGF mixture to the mechanical shear force.

In one embodiment, a method of making a molded article is disclosed, themethod including: providing a forming tool having a three-dimensionalshape having a forming portion, bringing said forming portion intocontact with a cellulose composition so that said forming portion iscovered with a wet layer of pulp; and dewatering the layer of pulp onthe forming tool to achieve the molded article, wherein the cellulosecomposition includes cellulose pulp and an enhanced cellulose nanonbrilbinder according to the present disclosure.

In one embodiment, another method of making a molded article isdisclosed, the method including: providing a forming tool having athree-dimensional shape having a finning portion, bringing the formingportion into contact with a cellulose composition so that said formingportion is covered with a wet layer of pulp; and dewatering the layer ofpulp on the forming tool to achieve the molded article, wherein thecellulose composition includes allulose pulp and a barrier formulationaccording to the present disclosure.

In one embodiment, another method of making a molded article isdisclosed, the method including: providing a forming tool having athree-dimensional shape having a forming portion, bringing the formingportion into contact with a cellulose composition so that said formingportion is covered with a wet layer of pulp; dewatering the layer ofpulp on the forming tool to obtain an intermediate molded article; andcoating a surface of the intermediate molded article with a barrierformulation according to the present disclosure by a process ofimmersion, spraying, painting, printing, or any combination of any ofthese processes to achieve the molded article.

In one aspect, the method of making the molded article includesconducting the dewatering at temperatures >100° C. to achieve a drycontent of at least about 70 wt. %, preferably at least about 80 wt. %.

In one aspect, the layer of pulp present on the forming tool isdewatered by means of press-drying performed at temperatures >100° C.,preferably at temperatures between about 120 to 250° C. or morepreferably between about 150 to 220° C.

In one aspect, the cellulose composition for the method of making themolded articles comprises a fiber mixture consisting essentially ofchemithermomechanical pulp (CTMP), thermomechanical pulp (TMP), chemicalpulp or semichemical pulp, or a combination thereof. The pulps can beeither bleached or unbleached.

In one aspect, the forming tool is porous or perforated so that watercan be removed during forming during a dewatering/drying step.

In one aspect, the method of making the molded article further includescoating a surface of the molded article with a barrier formulationcomprising the SGF blend by a process of immersion, spraying, painting,printing, or any combination of any of these processes.

In one aspect, the coating of the surface of the molded article with thebarrier formulation takes place while the molded article is anintermediate molded article having a relatively high aqueous content anda fiber content of about 20 to 50 wt. %, preferably about 30 to 40 wt.%.

In one embodiment, the disclosure provides a cellulose-based productobtained according to any of the methods disclosed herein, which is athree dimensional molded product, such as a molded food packagingproduct, made from cellulose fibers.

In one aspect, the three dimensional shape obtained by the methods ofmaking the molded article is not particularly limited.

In one aspect, examples of the three dimensional shape are a bowl, acup, a plate, a fork, a spoon, or a knife.

In some embodiments, the barrier formulation consists essentially of CNFand the SGF blend.

In some embodiments, a weight ratio in the barrier formulation of CNF toSGF blend is from about 20:1 to about 1:5. In some embodiments, theweight ratio may be about 5:1 to about 1:5.

In some embodiments, when a total weictht of the barrier formulation isconsidered to be 100% by weight, the barrier formulation includes about4% by weight to about 96% by weight of CNF, and about 4% by weight toabout 96% by weight of the SGF blend. In some embodiments, the amount ofthe CNF can be about 10% by weight to about 70% by weight. In someembodiments, the amount of the SGF blend can be about 30% by weight toabout 90% by weight.

In some embodiments, the barrier formulation further includes one ormore prolamins.

In some embodiments, the one or more prolamins are selected from wheat(gliadin), barley (hordein), rye (secalin), corn (zein), sorghum(kafirin), and/or oats (avenin).

In some embodiments, the cellulose-based material includes cellulosefiber suitable for making paper, and the aqueous mixture or dispersionis a papermaking furnish or stock.

In some embodiments, the molded article exhibits a water contact angleof equal to or greater than 90°, equal to or greater than 100°, equal toor greater than 110°, or equal to or greater than 120°.

In some embodiments, the molded article exhibits TAPPI T 559 KIT testvalue of from 3 to 12.

In some embodiments, the molded article exhibits reduced permeability togases (referred to as “gas resistance”) (e.g., resistance to oxygen,nitrogen, and carbon dioxide). In some aspects, the gas resistance is areduced permeability to oxygen.

In some embodiments, the molded article exhibits a water contact angleof equal to or greater than 90° and/or a TAPPI T 559 KIT test value offrom 3 to 12 in the absence of any secondary hydrophobes.

In some embodiments, the barrier formulation is in the form of anemulsion.

In some embodiments, the barrier formulation is a stable aqueouscomposition.

In another embodiment, a method of making a cellulose-based producthaving a barrier property is provided, the method including: obtaining afurnish that includes an aqueous mixture of cellulose fiber; adding theSGF blend to the furnish; adding CNF to the furnish; and adding aretention aid to the furnish for aiding in the retention of the SGFblend on the cellulose fiber.

In some embodiments, one or more charged polymers can be added in thewet-end to aid in the retention of the SFAE on the cellulose-basedmaterial. The one or more charged polymers may include one or morecationic polymers, anionic polymers, nonionic polymers, and/orzwitterionic polymers. In some embodiments, the charged polymer includesa combination of a relatively low molecular weight cationic polymer anda relative high molecular weight anionic polymer.

In some embodiments, the charged polymer consists of one or morecationic polymer. The one or more cationic polymer may include apolyacrylamide. The polyacrylamide may include polyDADMAC (polydiallyldimethylammonium chloride) or alum (aluminum sulfate).

In some embodiments, one or more prolamins can be added in the wet-endto aid in the retention of the SGF blend, CNF, and/or enhanced CNF onthe cellulose-based material.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Before the present compositions, methods, and methodologies aredescribed in more detail, it is to be understood that the disclosure isnot limited to particular compositions, methods, and experimentalconditions described, as such compositions, methods, and conditions mayvary. It is also to be understood that the terminology used herein isfor purposes of describing particular embodiments only, and is notintended to be limiting, since the scope of the present invention willbe limited only in the appended claims.

As used in this specification and the appended claims, the singularforms “a,” “an,” and “the” include plural references unless the contextclearly dictates otherwise. Thus, for example, references to “asaccharide fatty acid ester” includes one or more saccharide fatty acidesters and/or compositions of the type described herein which willbecome apparent to those persons skilled in the art upon reading thisdisclosure and so forth.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this disclosure belongs. Any methods and materialssimilar or equivalent to those described herein may be used in thepractice or testing of the disclosure, as it will be understood thatmodifications and variations are encompassed within the spirit and scopeof the instant disclosure.

The present disclosure provides an enhanced cellulose nanofibril binder.

Cellulose nanofibrils (also referred to herein as CNF) and their methodof production are well known in the art.

The CNF for use in the embodiments of the present disclosure is notparticularly limited. The CNF can be commercially obtained, or the CNFcan be made by known methods, which typically include subjecting asource of cellulose fibers (e.g., woodpulp) to a mechanical shearingforce.

The properties of the CNF are not particularly limited. The CNF may havetypical fibril widths of about 5 to 20 nanometers, and may have lengthsof several micrometers.

In some embodiments, the enhanced CNF can be obtained by contactingconventionally made CNF with an SGF blend and allowing the SGF blend tobind to the CNF. In other embodiments, the enhanced CNF can be madeobtained by subjecting a source of cellulose fibers (e.g., woodpulp) toa mechanical shearing stress while the CNF is in mixture with an SGFblend.

As noted above, the enhanced CNF provides benefits compared toconventionally used CNF, such as maintaining or increasing the drainagerate of the fiber mat from the slurry and reduced agglomeration of theCNF.

The present disclosure provides methods for imparting a barrier propertyto a cellulose-based material. The methods include contacting thecellulose-based material with a barrier formulation for imparting thebarrier property, and binding the barrier formulation to a surface ofthe cellulose-based material to obtain a bound cellulose-based materialhaving the barrier property, wherein the barrier property is one or moreselected from the group consisting of water resistance, gas resistance,and lipid resistance. The barrier formulation may include the enhancedCNF, or the barrier formulation may include the enhanced CNF and the SGFblend.

The methods of the present disclosure can provide a solvent-free,bio-based, high temperature-tolerant barrier (or barrier coating) foroil and grease (OGR), water, and/or gases (e.g., oxygen, nitrogen, andcarbon dioxide) and/or formed fiber (e.g., molded) products having theseproperties.

Another aspect of the present disclosure is that the barrier coatingscan be configured to provide improved water resistance and lipid(oil/grease) resistance without the use of PFAS. These barrierproperties can be provided by the SGF blend (see, e.g., the '073publication, the '953 publication, the '923 application, the '499application, the '433 application, and the '097 application, all ofwhich have been incorporated herein by reference).

In some embodiments, the enhanced CNF can be used on the wet end of thepapermaking process by adding the enhanced CNF directly into thepapermaking furnish. Alternatively, in other embodiments, a combinationof CNF and the SGF blend can be added directly into the papermakingfurnish to obtain similar benefits.

One or more charged polymers, such as polyDADMAC or polyacrylamide,could also be added to the furnish as a retention aid for promoting theabsorption of the SGF blend and/or the CNF onto the cellulosic surfaces.In some aspects, the charged polymer can be used to control theelectrostatic charge of the formulation containing the SGF blend.

In other embodiments, prolamins can be used as a binder. This isexplained, for example, in U.S. provisional application No. 63/044,820filed Jun. 26, 2020 (hereinafter “the '820 application), which isincorporated herein by reference in its entirety.

Prolamins may be used as a binder not only for the SGF blend and/or theCNF, but also for conventional pigments added to a papermaking furnish.Pigments are typically relatively small and charged on their surfaces,including their edges. Thus, the pigments can easily be caught up in(and selectively retained by) the prolamin matrix.

In addition to being added directly into the papermaking furnish, thebarrier formulations can be coated onto a cellulose-based material orsubstrate (e.g., an already formed paper product) by immersion,spraying, painting, printing, extrusion coating, metering or anycombination of any of these processes. The barrier formulation maycontain the enhanced CNF in a sufficient amount to impart a desiredwater resistance and/or OGR to the cellulose-based material.

Alternatively, the barrier formulation may contain CNF and the SGF blendin suitable amounts to impart a desired water resistance and/or OGR tothe cellulose-based material.

Alternatively, the barrier formulation may contain the enhanced CNF andthe SGF blend in suitable amounts to impart a desired water resistanceand/or OGR to the cellulose-based material.

In the present disclosure, the interaction between the SGF blend and theCNF may be by ionic, hydrophobic, van der Waals interaction, covalentbonding, or a combination thereof. As used herein, “bind”, includinggrammatical variations thereof, means to cohere or cause to cohereessentially as a single mass, and may refer to ionic, hydrophobic, vander Waals interaction, or covalent bonding, or a combination thereof.

In the present disclosure, the interaction between the SGF blend and thecellulose-based material may be by ionic, hydrophobic, van der Waalsinteraction, covalent bonding, or a combination thereof.

In the present disclosure, the interaction between the enhanced CNF andthe cellulose-based material may be by ionic, hydrophobic, van der Waalsinteraction, covalent bonding, or a combination thereof.

In some embodiments, the barrier formulation may also contain one ormore conventional binders used in papermaking, such as latex, PvOH, andstarch.

As used herein, “cellulosic” means natural, synthetic, or semisyntheticmaterials that can be molded or extruded into objects (e.g., bags,sheets) or films or filaments, which may be used for making such objectsor films or filaments, that is structurally and functionally similar tocellulose, e.g., coatings and adhesives (e.g., carboxymethylcellulose).In another example, cellulose, a complex carbohydrate (C₆H₁₀O₅)_(n) thatis composed of glucose units, which forms the main constituent of thecell wall in most plants, is cellulosic.

Examples of the cellulosic material (or cellulose-based material) foruse herein can be cellulose fibers conventionally used in the paperindustry, microfibrillated cellulose (MFC), nanofibrilated cellulose (orCNF), or cellulose nanocrystals.

As used herein, “coating weight” is the weight of a material (wet ordry) applied to a substrate. It is expressed in pounds per specifiedream or grams per square meter

As used herein, “effect”, including grammatical variations thereof,means to impart a particular property to a specific material.

As used herein, “hydrophobe” means a substance that does not attractwater. For example, waxes, rosins, resins, saccharide fatty acid esters,fatty acid salts, glycerides having long fatty acid chains; di- andtriglycerides, diketenes, shellacs, vinyl acetates, PLA, PEI, oils,fats, lipids, other water repellant chemicals or combinations thereofare hydrophobes.

As used herein, “hydrophobicity” means the property of beingwater-repellent, tending to repel and not absorb water.

As used herein, “lipid resistance” or “lipophobicity” means the propertyof being lipid-repellent, tending to repel and not absorb lipids,grease, fats and the like. In a related aspect, the grease resistancemay be measured by a “3M KIT” test, a TAPPI T559 Kit test, or a Cobb oiltest.

As used herein, “cellulose-containing material” or “cellulose-basedmaterial” means a composition which consists essentially of cellulose.For example, such material may include, but is not limited to, paper,paper sheets, paperboard, paper pulp, a carton for food storage,parchment paper, cake board, butcher paper, release paper/liner for apressure sensitive adhesive, a bag for food storage, a shopping bag, ashipping bag, bacon board, insulating material, tea bags, containers forcoffee or tea, a compost bag, eating utensil, container for holding hotor cold beverages, cup, a lid, plate, a bottle for carbonated liquidstorage, gift cards, a bottle for non-carbonated liquid storage, filmfor wrapping food, a garbage disposal container, a food handlingimplement, a fabric fibre (e.g., cotton or cotton blends), a waterstorage and conveying implement, alcoholic or non-alcoholic drinks, anouter casing or screen for electronic goods, an internal or externalpiece of furniture, a curtain and upholstery.

As used herein, “fibers in solution” or “pulp” means a lignocellulosicfibrous material prepared by chemically or mechanically separatingcellulose fibers from wood, fiber crops or waste paper. In a relatedaspect, where cellulose fibers are treated by the methods as disclosedherein, the cellulose fibers themselves contain bound SFAE, glyceride,and/or FAS as isolated entities, and where the bound cellulose fibershave separate and distinct properties from free fibers (e.g., pulp- orcellulose fiber- or nanocellulose or microfibrillated cellulose-SFAEblend bound material would not form hydrogen bonds between fibers asreadily as unbound fibers).

As used herein, “repulpable” means to make a paper or paperboard productsuitable for crushing into a soft, shapeless mass for reuse in theproduction of paper or paperboard.

As used herein, “tunable”, including grammatical variations thereof,means to adjust or adapt a process to achieve a particular result.

As used herein, “water contact angle” means the angle measured through aliquid, where a liquid/vapor interface meets a solid surface. Itquantifies the wettability of the solid surface by the liquid. Thecontact angle is a reflection of how strongly the liquid and solidmolecules interact with each other, relative to how strongly eachinteracts with its own kind. On many highly hydrophilic surfaces, waterdroplets will exhibit contact angles of 0° to 30°. Generally, if thewater contact angle is larger than 90°, the solid surface is consideredhydrophobic. Water contact angle may be readily obtained using anOptical Tensiometer (see, e.g., Dyne Testing, Staffordshire, UnitedKingdom).

As used herein, “water vapour permeability” means breathability or atextile's ability to transfer moisture. There are at least two differentmeasurement methods. One, the MVTR Test (Moisture Vapour TransmissionRate) in accordance with ISO 15496, describes the water vaporpermeability (WVP) of a fabric and therefore the degree of perspirationtransport to the outside air. The measurements determine how many gramsof moisture (water vapor) pass through a square meter of fabric in 24hours (the higher the level, the higher the breathability).

In one aspect, TAPPI T 530 Hercules size test (i.e., size test for paperby ink resistance) may be used to determine water resistance. Inkresistance by the Hercules method is best classified as a directmeasurement test for the degree of penetration. Others classify it as arate of penetration test. There is no one best test for “measuringsizing.” Test selection depends on end use and mill control needs. Thismethod is especially suitable for use as a mill control sizing test toaccurately detect changes in sizing level. It offers the sensitivity ofthe ink float test while providing reproducible results, shorter testtimes, and automatic end point determination.

Sizing, as measured by resistance to permeation through or absorptioninto paper of aqueous liquids, is an important characteristic of manypapers. Typical of these are bag, containerboard, butcher's wrap,writing, and some printing grades.

This method may be used to monitor paper or board production forspecific end uses provided acceptable correlation has been establishedbetween test values and the paper's end use performance. Due to thenature of the test and the penetrant, it will not necessarily correlatesufficiently to be applicable to all end use requirements. This methodmeasures sizing by rate of penetration. Other methods measure sizing bysurface contact, surface penetration, or absorption. Size tests areselected based on the ability to simulate the means of water contact orabsorption in end use. This method can also be used to optimize sizechemical usage costs.

As used herein, “oxygen permeability” means the degree to which apolymer allows the passage of a gas or fluid. Oxygen permeability (Dk)of a material is a function of the diffusivity (D) (i.e., the speed atwhich oxygen molecules traverse the material) and the solubility (k) (orthe amount of oxygen molecules absorbed, per volume, in the material).Values of oxygen permeability (Dk) typically fall within the range10-150×10⁻¹¹ (cm² ml O₂)/(s ml mmHg). A semi-logarithmic relationshiphas been demonstrated between hydrogel water content and oxygenpermeability (Unit: Barrer unit). The International Organization forStandardization (ISO) has specified permeability using the SI unithectopascal (hPa) for pressure. Hence Dk=10⁻¹¹ (cm² ml O₂) /(s ml hPa).The Barrer unit can be converted to hPa unit by multiplying it by theconstant 0.75.

As used herein “biodegradable”, including grammatical variationsthereof, means capable of being broken down especially into innocuousproducts by the action of living things (e.g., by microorganisms).

As used herein, “recyclable”, including grammatical variations thereof,means a material that is treatable or that can be processed (with usedand/or waste items) so as to make said material suitable for reuse.

As used herein, “Gurley second” or “Gurley number” is a unit describingthe number of seconds required for 100 cubic centimeters (deciliter) ofair to pass through 1.0 square inch of a given material at a pressuredifferential of 4.88 inches of water (0.176 psi) (ISO5636-5:2003)(Porosity). In addition, for stiffness, “Gurley number” is aunit for a piece of vertically held material measuring the forcerequired to deflect said material a given amount (1 milligram of force).Such values may be measured on a Gurley Precision Instruments device(Troy, New York).

HLB—The hydrophilic-lipophilic balance of a surfactant is a measure ofthe degree to which it is hydrophilic or lipophilic, determined bycalculating values for the different regions of the molecule.

Griffin's method for non-ionic surfactants as described in 1954 works asfollows:

HLB=20*M _(h) /M

-   -   where M_(h) is the molecular mass of the hydrophilic portion of        the molecule, and M is the molecular mass of the whole molecule,        giving a result on a scale of 0 to 20. An HLB value of 0        corresponds to a completely lipophilic/hydrophobic molecule, and        a value of 20 corresponds to a completely hydrophilic/lipophobic        molecule.

The HLB value can be used to predict the surfactant properties of amolecule:

-   -   <10: Lipid-soluble (water-insoluble)    -   >10: Water-soluble (lipid-insoluble)    -   1.5 to 3: anti-foaming agent    -   3 to 6: W/O (water in oil) emulsifier    -   7 to 9: wetting and spreading agent    -   13 to 15: detergent    -   12 to 16: O/W (oil in water) emulsifier    -   15 to 18: solubiliser or hydrotrope.

In some embodiments, the HLB values for the SFAE/glyceride/FAS blend (orthe entire formulation comprising said blend) as disclosed herein may bein the lower range. In some embodiments, the HLB values for theSFAE/glyceride/FAS blend (or the entire formulation comprising saidblend) as disclosed herein may be in the middle to higher ranges.

As used herein, “SEFOSE®” denotes a sucrose fatty acid ester made fromsoybean oil (soyate) which is commercially available from Procter &Gamble Chemicals (Cincinnati, OH) under the trade name SEFOSE 1618U (seesucrose polysoyate below), which contains one or more fatty acids thatare unsaturated. SEFOSE® is an exemplary SFAE for use in the methods andbarrier formulations of the present disclose.

As used herein, “soyate” means a mixture of salts of fatty acids fromsoybean oil. The SFAE for use in the methods and barriers formulas ofthe present disclosure may include or be derived from “soyate.”

As used herein, “oilseed fatty acids” means fatty acids from plants,including but not limited to soybeans, peanuts, rapeseeds, barley,canola, sesame seeds, cottonseeds, palm kernels, grape seeds, olives,safflowers, sunflowers, copra, corn, coconuts, linseed, hazelnuts,wheat, rice, potatoes, cassavas, legumes, camelina seeds, mustard seeds,and combinations thereof. The fatty acid chains of theSFAE/glyceride/FAS blend can be oilseed fatty acids.

As used herein “wet strength” means the measure of how well a web offibers holding paper together (or other three-dimensional, solid,cellulose-based product) can resist a force of rupture when the paper iswet. The wet strength may be measured using a Finch Wet Strength Devicefrom Thwing-Albert Instrument Company (West Berlin, N.J.). Where the wetstrength is typically effected by wet strength additives such as kymene,cationic glyoxylated resins, polyamidoamine-epichlorohydrin resins,polyamine-epichlorohydrin resins, including epoxide resins. Inembodiments, the barrier formulation coated cellulose-based material asdisclosed herein effects such wet strength in the absence of suchadditives.

As used herein “wet” means covered or saturated with water or anotherliquid.

The methods disclosed herein may include an additional step of exposingthe contacted cellulose-based material to heat, radiation, a catalyst ora combination thereof for a sufficient time to bind the SGF blend, CNF,and/or enhanced CNF to the cellulose-based material. In a relatedaspect, such radiation may include, but is not limited to UV, IR,visible light, or a combination thereof. In another related aspect, thereaction may be carried out at room temperature (i.e., 25° C.) to about150° C., about 50° C. to about 100° C., or about 60° C. to about 80° C.

As used herein, the term “natural waxes” refers to relatively highmolecular weight/high melting point materials. Specific examples of“natural waxes” include, for example, biowaxes obtained from renewableresources, such as vegetable oils, fatty acids, and fatty esters, etc.,(see, e.g.,https://www.researchgate.net/publication/318385619_High_Quality_Biowaxes_from_Fatty_Acids_and_Fatty_Esters_Catalyst_and_Reaction_Mechanism_for_Accompanying_Reactions;andhttps://www.researchgate.net/figure/a-Preparation-of-canola-PFFA-18-biowax-b-Preparation-of-nanocellulose-from-canola_fig1_306527797).

As used herein, the term “cellulose crosslinkers” means known cellulosecrosslinkers such as glyoxal, and small reactive dialdehydes oranhydrides.

The term “glycerides” as used herein has its common meaning and refersto acylglycerols, which are esters formed from glycerol and fatty acids.Glycerol has three hydroxyl functional groups, which can be esterifiedwith one, two, or three fatty acids to form mono-, di-, andtriglycerides. These structures can vary in their aliphatic chain asthey can contain different carbon numbers, different degrees ofunsaturation, and different configurations and positions of olefins.

The glycerides may be obtained by esterification with substantially purefatty acids by known processes of esterification. The glycerides canalso be extracted from plant oils and animal fats by known methods ofextraction.

The term “fatty acid” as used herein has its common meaning and refersto a carboxylic acid with an aliphatic chain, which may be saturated orunsaturated. The term fatty acid as used herein may refer to the fattyacid group bound to the glycerol residue of the glyceride.

The fatty acid groups of the glycerides can be any known fatty acid. Inpreferred embodiments, the fatty acid is known to be present in food, isedible, and/or is approved by the FDA. In some embodiments, the fattyacids are obtained from oilseeds. In other embodiments, the fatty acidsare obtained from other sources of naturally edible fats and oil.

The fatty acids of the glycerides can be independently selected from oneor more saturated fatty acids, one or more monounsaturated fatty acids,and/or one or more polyunsaturated fatty acids. By independently, thismeans, for example, that a triglyceride may comprise three differentfatty acid groups attached to the glycerol residue.

Exemplary saturated fatty acids for use in the formulations/compositionsof the disclosure can be selected from butyric acid (butanoic acid),caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid(decanoic acid), lauric acid, (dodecanoic acid), myristic acid(tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid(octadecanoic acid), arachidic acid (icosanoic acid), behenic acid(docosanoic acid), or lignoceric acid (tetracosanoic acid).

Exemplary monounsaturated fatty acids for use in theformulations/compositions of the disclosure can be selected fromcaproleic acid, (dec-9-enoic acid), lauroleic acid ((Z)-dodec-9-enoicacid), myristoleic acid ((Z)-tetradec-9-enoic acid), palmitoleic acid((Z)-hexadec-9-enoic acid), oleic acid ((Z)-octadec-9-enoic acid),elaidic acid ((E)-octadec-9-enoic acid), vaccenic acid((E)-octadec-11-enoic acid), gadoleic acid ((Z)-icos-9-enoic acid),erucic acid ((Z)-docos-13-enoic acid), brassidic acid((E)-docos-13-enoic acid), or nervonic acid ((Z)-tetracos-15-enoicacid).

Exemplary polyunsaturated fatty acids for use in theformulations/compositions of the disclosure can be selected fromlinoleic acid (LA) ((9Z,12Z)-octadeca-9,12-dienoic acid),alpha-Linolenic acid (ALA) ((9Z,12Z,15Z)-octadeca-9,12,15-trienoicacid), gamma-Linolenic acid (GLA) ((6Z,9Z,12Z)-octadeca-6,9,12-trienoicacid), columbinic acid ((5E,9E,12E)-octadeca-5,9,12-trienoic acid),stearidonic acid ((6Z,9Z,12Z,15Z)-octadeca-6,9,12,15-tetraenoic acid),mead acid ((5Z,8Z,11Z)-icosa-5,8,11-trienoic acid), dihomo-y-linolenicacid (DGLA) ((8Z,11Z,14Z)-icosa-8,11,14-trienoic acid), arachidonic acid((5Z,8Z,11Z,14Z)-icosa-5,8,11,14-tetraenoic acid), eicosapentaenoic acid(EPA) ((5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentaenoic acid),docosapentaenoic acid (DPA)((7Z,10Z,13Z,16Z,19Z)-docosa-7,10,13,16,19-pentaenoic acid),docosahexaenoic acid (DHA)((4Z,7Z,10Z,13Z,16Z,19Z)-docosa-4,7,10,13,16,19-hexaenoic acid).

In some embodiments, the one or more glycerides may include a blend ofone or more monoglycerides, one or more diglycerides, and/or one or moretriglycerides. In this regard, the mono-, di-, and triglycerides can beblended in any weight ratio. That is, any one of the mono-, di-, ortriglycerides could be the major glyceride component of the formulationby weight (that is, greater than 50% by weight when a total weight ofglycerides is considered to be 100% by weight). In other embodiments,the formulation does not include a monoglyceride; does not include adiglyceride; or does not include a triglyceride.

The one or more glycerides may vary in their fatty acid alkyl groups.For example, the one or more glycerides may contain fatty acid groupshaving different carbon numbers, different degrees of unsaturation,and/or different configurations and positions of olefins. The pluralityof glycerides may include tripalmitin and/or tristearin.

In some embodiments, the glycerides may include a combination of one ormore water insoluble glycerides (e.g., as noted above, triglycerides aretypically strongly nonpolar and hydrophobic) and one or more watersoluble glycerides (in any weight ratio from 0.1:99.9 to 99.9:0.1); oronly insoluble glycerides; or only insoluble glycerides. The solubilityof the glyceride can be determined, for example, by its HLB value.

A person of ordinary skill in the art will appreciate that the HLB valueof the one or more glycerides can be selected by varying one or more ofthe parameters of the glycerides noted above. In this regard, when aplurality of glycerides are used, each glyceride may have be chosen tohave similar or different HLB values (e.g., lower range used incombination with higher range).

The term “fatty acid salt” (or “FAS”) as used herein has its commonmeaning and refers to a salt of any one or more of the fatty acidsdisclosed herein above. Exemplary cations for the fatty acid saltsinclude but are not limited to calcium, potassium, and sodium salts. Thefatty acid salts can be synthesized by known methods or extracted fromplant oils or animal fats by known methods. One exemplary processcomprises adding sodium hydroxide to fatty acids found in animal fats orplant oils (such as from oilseeds). For example, sodium palmitate can beobtained from palm oil.

The one or more fatty acid salts may include one or more calcium,potassium or sodium salts. The calcium, potassium or sodium salts offatty acids can be obtained from a naturally occurring source, such asoil seeds. The one or more fatty acid salts can include one or moreselected from sodium oleate, sodium stearate, sodium palmitate, calciumoleate, calcium stearate, or calcium palmitate.

In some embodiments, the SGF blend may contain only one or moreglycerides, may contain only one or more fatty acid salts, or maycontain both one or more glycerides and one or more fatty acid salts.When the SGF blend contains both one or more glycerides and one or morefatty acid salts, the weight ratio of glycerides to fatty acid salts canbe from about 0.1:99.9 to about 99:0.1, from about 10:90 to about 90:10,from about 20:80 to about 80:20, from about 35:65 to about 65:35, fromabout 40:60 to about 60:40, from about 45:55 to about 55:45, or about50:50.

The weight ratio of the SFAE in the SGF blend may be 0:100 to 100:0 orany weight ratio therebetween (e.g., 1:99; 5:95; 10:90; 20:80; 30:70;40:60; 50:50; 60:50; 70:30; 80:20; 90:10; 95:5; 99:1).

The weight ratio of the glycerides in the SGF blend may be 0:100 to100:0 or any weight ratio therebetween (e.g., 1:99; 5:95; 10:90; 20:80;30:70; 40:60; 50:50; 60:50; 70:30; 80:20; 90:10; 95:5; 99:1).

The weight ratio of the fatty acid salts in the SGF blend may be 0:100to 100:0 or any weight ratio therebetween (e.g., 1:99; 5:95; 10:90;20:80; 30:70; 40:60; 50:50; 60:50; 70:30; 80:20; 90:10; 95:5; 99:1).

The weight ratio of the natural waxes in the SGF blend may be 0:100 to100:0 or any weight ratio therebetween (e.g., 1:99; 5:95; 10:90; 20:80;30:70; 40:60; 50:50; 60:50; 70:30; 80:20; 90:10; 95:5; 99:1).

The weight ratio of the cellulose crosslinkers in the SGF blend may be0:100 to 100:0 or any weight ratio therebetween (e.g., 1:99; 5:95;10:90; 20:80; 30:70; 40:60; 50:50; 60:50; 70:30; 80:20; 90:10; 95:5;99:1).

At a sufficient concentration, and based on the selection of the blend,the binding of the SGF blend alone is enough to make the contactedsubstrate hydrophobic: i.e., hydrophobicity is achieved in the absenceof the addition of waxes, rosins, resins, diketenes, shellacs, vinylacetates, PLA, PEI, oils, other water repellant chemicals orcombinations thereof (i.e., secondary hydrophobes), including that otherproperties such as, inter alia, strengthening, stiffing, and bulking ofthe cellulose-based material is achieved by glyceride/fatty acid saltbinding alone.

The use of CNF alone as a binder has also been shown to increase thehydrophobicity of the contacted substrate.

Saturated SFAE, glycerides, and fatty acid salts are typically solids atnominal processing temperatures, whereas unsaturated SFAE, glycerides,and fatty acid salts are typically liquids. This permits the formationof uniform, stable dispersions of saturated glycerides and fatty acidsalts in aqueous coatings without significant interactions orincompatibilities with other coating components, which are typicallyhydrophilic. In addition, this dispersion allows for high concentrationsof saturated glycerides and fatty acid salts to be prepared withoutadversely affecting coating rheology, uniform coating application, orcoating performance characteristics. The coating surface will becomehydrophobic when the particles of saturated glycerides and fatty acidsalts melt and spread upon heating, drying and consolidation of thecoating layer. The natural waxes of the present disclosures are alsosolids at nominal processing temperatures.

Saccharide fatty acid esters of all saccharides, including mono-,di-saccharides and tri-saccharides, are adaptable for use in connectionwith aspects of the present disclosure. The saccharide fatty acid estermay be a mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octaester,and combinations thereof, including that the fatty acid moieties may besaturated, unsaturated or a combination thereof.

The SFAE may comprise or consist essentially of sucrose esters of fattyacids.

Many methods are known and available for making or otherwise providingthe SFAE of the present disclosure, and all such methods are believed tobe available for use within the broad scope of the present disclosure.For example, in certain embodiments it may be preferred that the fattyacid esters are synthesized by esterifying a saccharide with one or morefatty acid moieties obtained from oil seeds including but not limitedto, soybean oil, sunflower oil, olive oil, canola oil, peanut oil, andmixtures thereof.

The SFAE may comprise a saccharide moiety, including but not limited toa sucrose moiety, which has been substituted by an ester moiety at oneor more of its hydroxyl hydrogens. In a related aspect, disaccharideesters for use in this disclosure can have the structure of Formula I ofthe '073 publication, which is incorporated herein by reference.

Suitable disaccharides for the SFAE may also include xylose, glucose,raffinose, maltodextrose, galactose, combinations of glucose,combinations of fructose, maltose, lactose, combinations of mannose,combinations of erythrose, isomaltose, isomaltulose, trehalose,trehalulose, cellobiose, laminaribiose, chitobiose and combinationsthereof.

In other embodiments, a starch fatty acid ester can be used, where thestarch may be derived from any suitable source such as dent corn starch,waxy corn starch, potato starch, wheat starch, rice starch, sago starch,tapioca starch, sorghum starch, sweet potato starch, and mixturesthereof.

For use in the compositions of the present disclosure, the SFAEcompounds may have a high degree of substitution. In some embodiments,the saccharide fatty acid ester is a sucrose polysoyate.

The SFAE can be produced in the manner disclosed in the '073application. For example, saccharide fatty acid esters may be made byesterification with substantially pure fatty acids by known processes ofesterification. They can be prepared also by trans-esterification usingsaccharide and fatty acid esters in the form of fatty acid glyceridesderived, for example, from natural sources, for example, those found inoil extracted from oil seeds, for example soybean oil.Trans-esterification reactions providing sucrose fatty acid esters usingfatty acid glycerides are described, for example, in U.S. Pat. Nos.3,963,699; 4,517,360; 4,518,772; 4,611,055; 5,767,257; 6,504,003;6,121,440; and 6,995,232, and International Publication WO1992004361,herein incorporated by reference in their entireties.

The cellulose-based products generated by the methods disclosed hereincan be configured to exhibit greater hydrophobicity (or waterresistance) relative to the same cellulose-containing material withoutthe treatment. In a related aspect, the treated cellulose-containingmaterial exhibits greater lipophobicity (or OGR) relative to the samecellulose-containing material without the treatment. In a furtherrelated aspect, the treated cellulose-containing material may bebiodegradable, compostable, and/or recyclable. In one aspect, thetreated cellulose-containing material is both hydrophobic (waterresistant) and lipophobic (lipid resistant) (OGR).

The cellulose-based products of the present disclosure may have improvedmechanical properties compared to that same material untreated. Forexample, paper bags treated by the process as disclosed herein showincreased burst strength, Gurley Number, Tensile Strength and/or Energyof Maximum Load. In one aspect, the burst strength is increased by afactor of between about 0.5 to 1.0 fold, between about 1.0 and 1.1 fold,between about 1.1 and 1.3 fold, between about 1.3 to 1.5 fold. Inanother aspect, the Gurley Number increased by a factor of between about3 to 4 fold, between about 4 to 5 fold, between about 5 to 6 fold andabout 6 to 7 fold. In still another aspect, the Tensile Strain increasedby a factor of between about 0.5 to 1.0 fold, between about 1.0 to 1.1fold, between about 1.1 to 1.2 fold and between about 1.2 to 1.3 fold.And in another aspect, the Energy of Max Load increased by a factor ofbetween about 1.0 to 1.1 fold, between about 1.1 to 1.2 fold, betweenabout 1.2 to 1.3 fold, and between about 1.3 to 1.4 fold

The cellulose-containing material can be a base paper comprisingmicrofibrillated cellulose (MFC) or cellulose nanofiber (CNF) asdescribed for example in U.S. Pub. No. 2015/0167243 (incorporated hereinby reference in its entirety), where the MFC or CNF is added during theforming process and paper making process and/or added as a coating or asecondary layer to a prior forming layer to decrease the porosity ofsaid base paper. In embodiments, the resulting contacted base paper istuneably water and lipid resistant. In a related aspect, the resultingbase paper may exhibit a Gurley value of at least about 10-15 (i.e.,Gurley Air Resistance (sec/100 cc, 20 oz. cyl.)), or at least about 100,at least about 200 to about 350. In one aspect, the barrier coatingdisclosed herein may be a laminate for one or more layers or may provideone or more layers as a laminate or may reduce the amount of coating ofone or more layers to achieve the same performance effect (e.g., waterresistance, grease resistance, and the like). In a related aspect, thelaminate may comprise a biodegradable and/or composable heat seal oradhesive.

In embodiments, the SGF blend may be combined with one or more coatingcomponents for internal and surface sizing (alone or in combination),including but not limited to, pigments (e.g., clay, calcium carbonate,titanium dioxide, plastic pigment), binders (e.g., starch, soy protein,polymer emulsions, PvOH, casein), and additives (e.g., glyoxal,glyoxalated resins, zirconium salts, polyethylene emulsion,carboxymethyl cellulose, acrylic polymers, alginates, polyacrylate gums,polyacrylates, microbiocides, oil based defoamers, silicone baseddefoamers, stilbenes, direct dyes and acid dyes). In a related aspect,such components may provide one or more properties, including but notlimited to, building a fine porous structure, providing light scatteringsurface, improving ink receptivity, improving gloss, binding pigmentparticles, binding coatings to paper, base sheet reinforcement, fillingpores in pigment structure, reducing water sensitivity, resisting wetpick in offset printing, preventing blade scratching, improving gloss insupercalendering, reducing dusting, adjusting coating viscosity,providing water holding, dispersing pigments, maintaining coatingdispersion, preventing spoilage of coating/coating color, controllingfoaming, reducing entrained air and coating craters, increasingwhiteness and brightness, and controlling color and shade. It will beapparent to one of skill in the art that combinations may be varieddepending on the property(ies) desired for the final product

In a wet end application, the SGF blend may be present in the aqueousmixture or dispersion at a concentration of at least 0.025% (wt/wt) ofthe total cellulose fiber present in the dispersion. In related aspects,the SGF blend may be present at about 0.05% (wt/wt) to about 0.1%(wt/wt), about 0.1% (wt/wt) to about 0.5% (wt/wt), about 0.5% (wt/wt) toabout 1.0% (wt/wt), about 1.0% (wt/wt) to about 2.0% (wt/wt), about 2.0%(wt/wt) to about 3.0% (wt/wt), about 3.0% (wt/wt) to about 4.0% (wt/wt),about 4.0% (wt/wt) to about 5.0% (wt/wt), about 5.0% (wt/wt) to about10% (wt/wt), or about 10% (wt/wt) to about 50% (wt/wt) of the totalfiber present.

In a wet end application, CNF may be present in the aqueous mixture ordispersion at a concentration of at least 0.025% (wt/wt) of the totalcellulose fiber present in the dispersion. In related aspects, the CNFmay be present at about 0.05% (wt/wt) to about 0.1% (wt/wt), about 0.1%(wt/wt) to about 0.5% (wt/wt), about 0.5% (wt/wt) to about 1.0% (wt/wt),about 1.0% (wt/wt) to about 2.0% (wt/wt), about 2.0% (wt/wt) to about3.0% (wt/wt), about 3.0% (wt/wt) to about 4.0% (wt/wt), about 4.0%(wt/wt) to about 5.0% (wt/wt), about 5.0%(wt/wt) to about 10% (wt/wt),about 10% (wt/wt) to about 20% (wt/wt), about 20% (wt/wt) to about 30%(wt/wt), about 30% (wt/wt) to about 40% (wt/wt), about 40% (wt/wt) toabout 50% (wt/wt), about 60% (wt/wt) to about 70% (wt/wt), about 70%(wt/wt) to about 80% (wt/wt), or about 80% (wt/wt) to about 90% (wt/wt)of the total fiber present.

In a wet end application, the enhanced CNF may be present in the aqueousmixture or dispersion at a concentration of at least 0.025% (wt/wt) ofthe total cellulose fiber present in the dispersion. In related aspects,the enhanced CNF may be present at about 0.05% (wt/wt) to about 0.1%(wt/wt), about 0.1% (wt/wt) to about 0.5% (wt/wt), about 0.5% (wt/wt) toabout 1.0% (wt/wt), about 1.0% (wt/wt) to about 2.0% (wt/wt), about 2.0%(wt/wt) to about 3.0% (wt/wt), about 3.0% (wt/wt) to about 4.0% (wt/wt),about 4.0% (wt/wt) to about 5.0% (wt/wt), about 5.0%(wt/wt) to about 10%(wt/wt), about 10% (wt/wt) to about 20% (wt/wt), about 20% (wt/wt) toabout 30% (wt/wt), about 30% (wt/wt) to about 40% (wt/wt), about 40%(wt/wt) to about 50% (wt/wt), about 60% (wt/wt) to about 70% (wt/wt),about 70% (wt/wt) to about 80% (wt/wt), or about 80% (wt/wt) to about90% (wt/wt) of the total fiber present.

As used herein, “coating weight” is the weight of a material (wet ordry) applied to a substrate. It is expressed in pounds per specifiedream or grams per square meter

In a coating application, the enhanced CNF may be present at a coatingweight of at least about 0.05 g/m² on the surface of the substrate. Inrelated aspects, the SGF blend may be present at a coating weight ofabout 0.05 g/m 2 to about 1.0 g/m², about 1.0 g/m² to about 2.0 g/m²,about 2 g/m² to about 3 g/m² 3 g/m² to about 4 g/m², about 4 g/m² toabout 5 g/m², about 5 g/m² to about 10 g/m², or about 10 g/m² to about20 g/m² on a surface of the cellulose-based material.

In a coating application, the SGF blend may be present at a coatingweight of at least about 0.05 g/m² on the surface of the substrate. Inrelated aspects, the SGF blend may be present at a coating weight ofabout 0.05 g/m² to about 1.0 g/m², about 1.0 g/m² to about 2.0 g/m²,about 2 g/m² to about 3 g/m² 3 g/m² to about 4 g/m², about 4 g/m² toabout 5 g/m², about 5 g/m² to about 10 g/m², or about 10 g/m² to about20 g/m² on a surface of the cellulose-based material.

In a coating application, the CNF may be present at a coating weight ofat least about 0.05 g/m² (gsm) on the surface of the cellulose-basedmaterial (or substrate). In related aspects, the CNF can be present at acoating weight of about 0.05 g/m² to about 1.0 g/m², about 1.0 g/m² toabout 2.0 g/m², about 2 g/m² to about 3 g/m², 3 g/m² to about 4 g/m²,about 4 g/m² to about 5 g/m², about 5 g/m² to about 10 g/m², about 10g/m² to about 20 g/m², or about 20 g/m² to about 30 g/m² on a surface ofthe cellulose-based material.

The hydrophobic barrier property might be imparted to the substrate bythe SGF blend and/or the enhanced CNF in the absence of any secondaryhydrophobes.

The barrier formulation may include one or more emulsifiers oremulsifying agents in a concentration sufficient to form an emulsion ofthe SGF blend and water and/or to form an emulsion of the enhanced CNFand water. Suitable emulsifiers or emulsifying agents include buffers,polyvinyl alcohol (PvOH), carboxymethyl cellulose (CMC), milk proteins,gelatins, starches, acetylated polysaccharides, alginates, carrageenans,chitosans, inulins, long chain fatty acids, waxes, agar, alginates,glycerol, gums, lecithins, poloxamers, mono-, di-glycerols, monosodiumphosphates, monostearate, propylene glycols, detergents, cetyl alcohol,glycerol esters, (saturated) ((poly)unsaturated) fatty acid methylesters, and combinations thereof.

The methods disclosed herein may include a step of predetermining acontent of the SGF blend and/or the components of the SGF blend to beincluded in the enhanced CNF. In some aspects, this step ofpredetermining can be performed prior to the preparing the enhanced CNF.The step of predetermining can be performed to achieve the desiredeffects. The step of predetermining can be performed to achieve adesired level of water resistance and/or a desired level of oil andgrease resistance when the enhanced CNF is used in a barrier formulationand/or added to the papermaking furnish on the wet end. In some aspects,the step of predetermining can be performed to increase dewatering rateof the furnish or fiber slurry. Increasing the dewatering rate improvesthe rate, for example, of producing a cellulose-based article. As notedabove, dewatering a slurry containing CNF is one of the biggest problemsdirected to use of CNF. The increased dewatering rate applies, forexample, to both the making of the enhanced CNF binder and the use ofthe enhanced CNF binder in a barrier formulation. Dewatering is wellknown in the papermaking industry, and is also explained in Smook, whichis incorporated herein by reference in its entirety elsewhere in thisdisclosure.

The methods disclosed herein may include a step of predetermining acontent of the SGF blend and/or predetermining the components of the SGFblend to be included in the barrier formulations. In some aspects, thisstep of predetermining can be performed prior to the preparing thebarrier formulation, or can be performed prior to the contacting thecellulose-based material with the formulation. The step ofpredetermining can be performed to achieve the desired effects. The stepof predetermining can be performed to achieve a desired level of waterresistance and/or a desired level of oil and grease resistance.

As noted above, the barrier formulations may include one or morepigments commonly used in the paper industry. The one or more pigmentscan be present in the formulation in a concentration of about 0.1% toabout 90% by weight based on a total weight of the formulation. In otheraspects, the concentration of the pigment can be from about 1% to 10% byweight, from about 11% to 20% by weight, from about 21% to 30% byweight, from about 31% to 40% by weight, from about 41% to 50% byweight, 51% to 60% by weight, 61% to 70% by weight, 71 to 80% by weight,81% to 90% by weight, or any other range between 0.1% to 90% by weight.The use of pigments is well known in the paper industry, and the pigmentconcentration can be chosen to vary the properties of the final product.Example pigments include clay, calcium carbonate, titanium dioxide,kaolin, talc, plastic pigment, silica, silicates, metal oxides, alumina,aluminates, and diatomaceous earth.

As noted above, the barrier formulation may include one or more chargedpolymers to aid in the retention of the enhanced CNF and/or the SGFblend on the cellulose-based substrate. The one or more charged polymersmay include one or more cationic polymers, anionic polymers, nonionicpolymers, and/or zwitterionic polymers. The charged polymer may includea combination of a relatively low molecular weight cationic polymer anda relative high molecular weight anionic polymer.

The charged polymer may consist of one or more cationic polymer. The oneor more cationic polymer may include a polyacrylamide. Thepolyacrylamide may include polyDADMAC (poly diallyldimethylammoniumchloride).

The cationic polymer may have a weight average molecular weight of500,000 to 10,000,000. In some aspects, the weight average MW is 500,000to 1,000,000, 1,000,001 to 2,000,000, 2,000,001 to 3,000,000, 3,000,001to 4,000,000, 4,000,001 to 5,000,000, 5,000,001 to 6,000,000, 6,000,001to 7,000,000, 7,000,001 to 8,000,000, 8,000,001 to 9,000,000, or9,000,001 to 10,0000. In some aspects, a blend of charged polymers areused to achieve a “bimodal”-type weight average MW using a combinationof charged polymers having any MW in the ranges above (e.g., a firstcharged polymer having a weight average MW of less than 1,000,000 usedin combination with a second charged polymer having a weight average MWgreater than 2,000,000; wherein the weight ratio of the first chargedpolymer to the second charged polymer is 10:90 to 90:10). In someembodiments, a concentration of the cationic polymer in the formulationis from about 0.01% to about 5% by weight, from about 0.01% to about 3%by weight, 0.05% to about 0.1% by weight, or from about 0.1% to about 1%by weight, or from about 1% to about 3% by weight when a total weight ofthe formulation is considered 100%. In some aspects, a weight ratio inthe formulation of the cationic polymer to the enhanced CNF is fromabout 0.1:99.9 to about 20:80, from 0.5:99.5 to about 15:85, from about1:99 to about 10:90, or from about 2.5:97.5 to about 7.5:92.5. In someaspects, a weight ratio in the formulation of the cationic polymer tothe SGF blend is from about 0.1:99.9 to about 20:80, from 0.5:99.5 toabout 15:85, from about 1:99 to about 10:90, or from about 2.5:97.5 toabout 7.5:92.5.

In some aspects, as noted above, prolamins can be used as the retentionaid of a barrier formulation including the enhanced CNF and/or the SGFblend instead of a charged polymer.

The barrier formulation may also include one or more conventionalpapermaking binders. Example binders include CNF, the enhanced CNF ofthe present disclosure, starch, polymers, polymer emulsions, PvOH,prolamins, or combinations thereof. In some aspects, the formulation maynot contain any binder other than the enhanced CNF.

The barrier formulation can be provided in the form of an emulsion. Theemulsion can be used as the barrier formulation of the methods of thepresent disclosure. In some aspects, the emulsion may not contain anyemulsifier other than an SGF blend. Alternatively, the emulsion caninclude about 0.01% to about 80% by weight of one or more emulsifiers.The emulsion may also include material for stabilizing the emulsion overa period of time (e.g., weeks, months, etc.), such as a nano ormicrofibrilized cellulose, a gum, or a thickening agent. A list ofexemplary emulsifiers is described above.

The cellulose-based material or substrate, which may be dried prior toapplication (e.g., at about 80-150° C.), may be treated with themodifying formulations by dipping, for example, and allowing the surfaceto be exposed to the composition for less than 1 second. The substratemay be heated to dry the surface, after which the modified material isready for use. In one aspect, according to the method as disclosedherein, the substrate may be treated by any suitable coating/sizingprocess typically carried out in a paper mill (see, e.g., Smook, G.,Surface Treatments in Handbook for Pulp & Paper Technologists, (2016),4^(th) Ed., Cpt. 18, pp. 293-309, TAPPI Press, Peachtree Corners, GAUSA, herein incorporated by reference in its entirety).

No special preparation of the cellulose-based material is necessary inpracticing this disclosure, although for some applications, the materialmay be dried before treatment. In embodiments, the methods as disclosedmay be used on any cellulose-based surface, including but not limitedto, a film, a rigid container, fibers, pulp, a fabric or the like. Inone aspect, the barrier formulations may be applied by conventional sizepress (vertical, inclined, horizontal), gate roll size press, meteringsize press, calender size application, tube sizing, on-machine,off-machine, single-sided coater, double-sided coater, short dwell,simultaneous two-side coater, blade or rod coater, gravure coater,gravure printing, flexographic printing, ink-jet printing, laserprinting, water box on a calender, and combinations thereof.

Depending on the source, the cellulose treated in the methods herein maybe paper, paperboard, pulp, softwood fiber, hardwood fiber, orcombinations thereof, nanocellulose, cellulose nanofibres, whiskers ormicrofibril, microfibrillated, cotton or cotton blends, cellulosenanocrystals, or nanofibrilated cellulose.

In addition, fibers and cellulose-based material modified as disclosedherein, may be repulped. Further, for example, water cannot be easily“pushed” past the low surface energy barrier into the sheet.

In embodiments, the amount of the barrier formulation applied issufficient to completely cover at least one surface of a substrate, suchas at least one surface of a cellulose-containing material. For example,in embodiments, the barrier formulation may be applied to the completeouter surface of a container, the complete inner surface of a container,or a combination thereof, or one or both sides of a base paper. In otherembodiments, the complete upper surface of a film may be covered by thebarrier formulation, or the complete under surface of a film may becovered by the barrier formulation, or a combination thereof. In someembodiments, the lumen of a device/instrument may be covered by thebarrier formulation or the outer surface of the device/instrument may becovered by the barrier formulation or a combination thereof.

In embodiments, the amount of barrier formulation applied is sufficientto partially cover at least one surface of a cellulose-based material.For example, only those surfaces exposed to the ambient atmosphere arecovered by the barrier formulation, or only those surfaces that are notexposed to the ambient atmosphere are covered by the barrier formulation(e.g., masking). As will be apparent to one of skill in the art, theamount of barrier formulation applied may be dependent on the use of thematerial to be covered. In one aspect, one surface may be coated with abarrier formulation and the opposing surface may be coated with an agentincluding, but not limited to, proteins, wheat glutens, gelatins,prolamins, soy protein isolates, starches, modified starches, acetylatedpolysaccharides, alginates, carrageenans, chitosans, inulins, long chainfatty acids, waxes, and combinations thereof. In a related aspect, thebarrier formulation can be added to a furnish, and the resultingmaterial on the web may be provided with an additional coating of thebarrier formulation (having the same or different composition as theformulation added on the wet end).

Any suitable coating process may be used to deliver any of the variousbarrier formulations in the course of practicing the methods. Inembodiments, the coating processes include immersion, spraying,painting, printing, and any combination of any of these processes, aloneor with other coating processes adapted for practicing the methods asdisclosed.

The permeability of a surface to various gases such as water vapour andgases (e.g., oxygen, nitrogen, and carbon dioxide) may also be alteredby the barrier formulations as the barrier function of the material isenhanced. The standard unit measuring permeability is the Barrer andprotocols to measure these parameters are also available in the publicdomain (ASTM std F2476-05 for water vapour and ASTM std F2622-8 foroxygen, for gas testing ingeneral—https://www.ametekmocon.com/products/searchbybrand/mocon. MOCONPermeation Testing Analyzers are recognized as the industry-leadingsolution for over 50 years and are the basis for many globalpermeability testing standards such as ASTM D3985 and ASTM F1249. Theextensive line of MOCON analyzers represent decades of technicalleadership and continuous innovation in partnership with our customers,distributors and institutions. Our MOCON Permeation Analyzers offer awide range of testing capabilities across the most diverse range ofproducts and materials”. . . ). In some aspects, permeability to vapoursand gases can be further reduced by adding one or more prolamins to thebarrier formulation.

In embodiments, materials treated according to the disclosed methodsdisplay a complete biodegradability as measured by the degradation inthe environment under microorganismal attack.

Various methods are available to define and test biodegradabilityincluding the shake-flask method (ASTM E1279-89(2008)) and theZahn-Wellens test (OECD TG 302 B).

Various methods are available to define and test compostabilityincluding, but not limited to, ASTM D6400.

The barrier coated product of the present disclosure may have a TAPPI T559 KIT test value of from about 3 to about 12, greater than 4, greaterthan 5, greater than 6, greater than 7, greater than 8, greater than 9,greater than 10, greater than 11, etc.

The barrier coated product of the present disclosure may have an HSTvalue of at least about 65 seconds, at least about 120 seconds, at leastabout 240 seconds, at least about 480 seconds, etc.

A surface of the barrier coated product of the present disclosure mayexhibit a water contact angle between about 60 to 120 degrees, of atleast about 90 degrees, at least about 100 degrees, at least about 110degrees, at least about 120 degrees, etc.

In some embodiments, the barrier formulation of the present disclosureforms a stable aqueous composition, the term “stable aqueouscomposition” is defined as an aqueous composition which is substantiallyresistant to viscosity change, coagulation, and sedimentation over atleast an 8-hour period when contained in a closed vessel and stored at atemperature in a range of from about 0 degrees C. to about 60 degrees C.Some embodiments of the barrier formulation are stable over at least a24-hour period, and often over at least a 6-month period.

In some embodiments, the barrier coated product obtained by the methodsof the present disclosure does not include a PFAS. In some embodiments,the barrier coated product of the present disclosure does not include aPFAS in the barrier coating.

In some embodiments, the barrier coated product obtained by the methodsof the present disclosure is folded into a three-dimensional shape andis contained within a sealed package. In these embodiments, the barrierlayer may be an exposed layer (or outer layer) within the inside of thepackage. The material of the package can be any conventional materialfor storing, shipping, selling, etc. a food or beverage product. Inthese embodiments, the sealed package may also contain therein a food orbeverage product. In these embodiments, the food or beverage product maycontact the barrier paper layer. The seal of the sealed package may be ahermetic seal.

In some embodiments, the barrier coated product obtained by the methodsof the present disclosure is compatible with traditional paper recyclingprograms: i.e., poses no adverse impact on recycling operations, likepolyethylene, polylactic acid, or wax coated papers do.

In some embodiments, the barrier coated product obtained by the methodsof the present disclosure is bio-based. As used herein, “bio-based” (or“biobased”) means a material intentionally made from substances derivedfrom living (or once-living) organisms. In a related aspect, materialcontaining at least about 50% of such substances is consideredbio-based. In some aspects, the barrier coated product obtained by themethods of the present disclosure may be entirely bio-based. In someaspects, the barrier formulations of the present disclosure may beentirely bio-based.

In some embodiments, the barrier coated product obtained by the methodsof the present disclosure is recyclable. As used herein, “recyclable”,including grammatical variations thereof, means a material that istreatable or that can be processed (with used and/or waste items) so asto make said material suitable for reuse.

In some embodiments, the barrier coated product of the presentdisclosure is biodegradable. As used herein “biodegradable”, includinggrammatical variations thereof, means capable of being broken downespecially into innocuous products by the action of living things (e.g.,by microorganisms).

EXAMPLES

In the following, although embodiments of the present disclosure aredescribed in further detail by means of Examples, the present disclosureis not limited thereto.

Example 1

Example 1 is a lab study regarding the use of CNF in molded pulpproducts with barrier properties.

The equipment used in Example 1 are as follows:

-   -   Buchner funnel—large (which is believed to be about 8″ diameter)    -   Vacuum flask    -   Lab vacuum pump    -   Spray bottle    -   Stop watch

The materials that may be used in Example 1 are as follows:

-   -   Bleached kraft pulp (50% SWK, 50% HWK) slurried at 1% solids    -   CNF slurry—0.5% solids    -   CNF slurry with 10% SE-15* added, 0.5% solids    -   SE-9**/SE 30*** emulsion, 1% solids    -   C-PAM (Cationic polyacrylamide), 0.1% solids    -   Cationic Coagulant, 0.1% solids    -   Pigment, 1% solids Capim DG Clay slurry from IMERYS.

*SE-15 was obtained from HANGZHOU UNION BIOTECHNOLOGY CO., LTD. SE-15 ismarketed as a sucrose fatty acid ester. SE-15 was analyzed and was foundto contain about 15 to 30% by weight saccharide fatty acid ester, about40 to 60% by weight glycerides, and a balance fatty acid salts plustrace components.

**SE-9 was obtained from ZHEJIANG SYNOSE TECH. SE-9 is marketed as asucrose fatty acid ester. SE-9 was analyzed and was found to be similarin composition to SE-15, except for having a higher glycerides contentand about 10 to 20% less sucrose ester.

***SE-30 was obtained from EAST CHEMSOURCES LIMITED. SE-30 is marketedas a sucrose fatty acid ester. SE-30 was analyzed and was found tocontain greater than 80% sucrose esters with a variety of substitutions.The remainder of the product was glycerides with relatively low (lessthan 5% by weight) salt.

The test procedure for Example 1 was as follows:

Blank or Control

-   -   (1) Add a sufficient quantity of bleached kraft slurry to the        Buchner funnel to produce a fiber pad with a grammage of 150        gsm. Note the volume of furnish used for future runs.    -   (2) Start vacuum pump once slurry has been added to Buchner        funnel.    -   (3) Note the time to drain furnish to the “wet line,” which is        the point during the drainage process where the surface of the        fiber slurry goes from shiny or “wet” look to a dull, textured        surface.    -   (4) Continue to apply vacuum to the wet sample for 10 seconds.    -   (5) Remove the wet mat from the Buchner funnel, and place the        wet mat between two blotters. Roll standard hand sheet roller        across blotters twice to press test sample.    -   (6) Removed pressed sample and place in a 100° C. oven until        dry.

Internally Treated (Wet End Application)

-   -   (1) Add one or more additives to an aliquot of furnish (volume        determined during the production of the control sample) slurry        and mix. See Table 1 below.    -   (2) Add a sufficient quantity of blended slurry to the Buchner        funnel to produce a fiber pad with a grammage of 150 gsm.    -   (3) Start vacuum pump once slurry has been added to Buchner        funnel.    -   (4) Note time to drain furnish to the “wet line.”    -   (5) Continue to apply vacuum to the wet sample for 10 seconds.    -   (6) Remove the wet mat from the Buchner funnel, and place the        wet mat between two blotters. Roll standard hand sheet roller        across blotters twice to press test sample.    -   (7) Remove pressed sample and place in a 100° C. oven until dry.

Spray Treated (Coating Formed Article)

-   -   (1) Add a sufficient quantity of bleached kraft slurry to the        Buchner funnel to produce a fiber pad with a grammage of 150        gsm.    -   (2) Start vacuum pump once slurry has been added to Buchner        funnel.    -   (3) Note time to drain furnish to the “wet line.”    -   (4) Spray a known amount of a dilute suspension of the additive        onto the surface of the wet mat. See Table 2 below.    -   (5) Continue to apply vacuum to the wet sample for 10 seconds.    -   (6) Remove the wet mat from the Buchner funnel, and place the        wet mat between two blotters. Roll standard hand sheet roller        across blotters twice to press test sample.    -   (7) Remove pressed sample and place in a 100 C oven until dry.

TABLE 1 Internal Treatment SE-9/SE-30 Run # ID CNF Blend C-PAM Cat. Coag1 Control 0 0 0.025 0.5 2 INT-1 1 0 0.025 0.5 3 INT-2 0 4 0.025 0.5 4INT-3 1 4 0.025 0.5

In Table 1, the additives are listed by their weight % on a dry basis.

TABLE 2 Spray Treatment SE-9/SE-30 Run # ID CNF Blend C-PAM Cat. Coag 5Control 0 0 0 0 6 SPR-1 2 0 0 0 7 SPR-2 0 4 0 0 8 SPR-3 2 4 0 0

In Table 2, the additives are listed by their weight % on a dry basis.

Based on experimental testing of the example embodiments, the data inTable 3 shows the improvement obtained in water resistance and/or oiland grease resistance. Water resistance has been tested using a waterCobb test adapted from Tappi Standard Test Method T 441 om-20 “WaterAbsorptiveness of Paper.” Oil and grease resistance has been testedusing a 3M KIT Test (Tappi Standard Test Method T 559 “Greaseresistance”) and an oil Cobb test using vegetable oil adapted from TappiStandard Test Method T 441 om-20.

TABLE 3 Oil Cobb Oil Cobb (2 min) Water Cobb test (Room Temp) (2 min) 3MKitt (85° C.) Run # ID g/cm² (Room Temp) Test g/cm² Internal Treatment 1Control 1280 790 0 2 INT-1 1185 850 0 3 INT-2 728 27 3 4 INT-3 95 20 4Spray Treatment 5 Control 868 1730 0 1244 6 SPR-1 22 1505 6 16 7 SPR-2588 165 3 764 8 SPR-3 15 81 6 17

While there have been shown and described fundamental novel features ofthe disclosure as applied to the preferred and exemplary embodimentsthereof, it will be understood that omissions and substitutions andchanges in the form and details of the disclosure may be made by thoseskilled in the art without departing from the spirit of the disclosure.Moreover, as is readily apparent, numerous modifications and changes mayreadily occur to those skilled in the art. For example, any feature(s)in one or more embodiments may be applicable and combined with one ormore other embodiments. Hence, it is not desired to limit the presentdisclosure to the exact construction and operation shown and describedand, accordingly, all suitable modification equivalents may be resortedto falling within the scope of the present disclosure as claimed. Inother words, although the embodiments of the disclosure have beendescribed with reference to the above examples, it will be understoodthat modifications and variations are encompassed within the spirit andscope of the disclosure. Accordingly, the invention is limited only bythe following claims.

All references disclosed herein are hereby incorporated by reference intheir entireties.

1. An enhanced cellulose nanofibril binder, comprising: cellulosenanofibrils (CNF); and an SGF blend bound to the CNF, wherein the SGFblend comprises one or more selected from the group consisting ofsaccharide fatty acid esters (SFAE), glycerides, fatty acid salts,natural waxes, and cellulose crosslinkers.
 2. The enhanced cellulosenanofibril binder according to claim 1, wherein the enhanced cellulosenanofibril binder consists essentially of the CNF and the SGF blend. 3.The enhanced cellulose nanofibril binder according to claim 1, wherein aweight ratio of the CNF to the SGF blend is 10:90 to 90:10.
 4. Theenhanced cellulose nanofibril binder according to claim 1, wherein aweight ratio of the CNF to the SGF blend is 40:60 to 60:40.
 5. Theenhanced cellulose nanofibril binder according to claim 1, wherein theenhanced cellulose nanofibril binder is obtained by: obtaining anaqueous mixture of cellulose nanofibrils (CNF); obtaining an aqueous SGFblend, the aqueous SGF blend comprising one or more selected from thegroup consisting of saccharide fatty acid esters (SFAE), glycerides,fatty acid salts, natural waxes, and cellulose crosslinkers; and mixingthe aqueous mixture of CNF with the aqueous SGF blend and allowing theCNF to bind to the SGF blend to obtain the enhanced cellulose nanofibrilbinder.
 6. The enhanced cellulose nanofibril binder according to claim5, further comprising reducing a water content of the CNF mixed with theaqueous SGF blend.
 7. The enhanced cellulose nanofibril binder accordingto claim 1, wherein the enhanced cellulose nanofibril binder is obtainedby: obtaining an aqueous mixture of cellulose pulp; obtaining an aqueousSGF blend, the aqueous SGF blend comprising one or more selected fromthe group consisting of saccharide fatty acid esters (SFAE), glycerides,fatty acid salts, natural waxes, and cellulose crosslinkers; mixing themixture of cellulose pulp with the aqueous SGF blend to obtain acellulose/SGF mixture; and subjecting the cellulose/SGF mixture tomechanical shear forces to obtain the enhanced cellulose nanofibrilbinder.
 8. (canceled)
 9. A barrier formulation comprising the enhancedcellulose nanofibril binder according to claim
 1. 10. A method of makinga cellulose-based article, the method comprising: adding the enhancedcellulose nanofibril binder according to claim 1 to an aqueouspapermaking furnish; and draining the water from the furnish to obtain afibrous web.
 11. The method of making a cellulose-based articleaccording to claim 10, further comprising molding the fibrous web into amolded article having a three-dimensional shape.
 12. A method forimparting a barrier property to a cellulose-based material, comprising:contacting the cellulose-based material with an aqueous barrierformulation for imparting the barrier property, the barrier formulationcomprising the enhanced cellulose nanofibril binder according to claim1; and binding the barrier formulation to a surface of thecellulose-based material to obtain a bound cellulose-based materialhaving the barrier property, wherein the barrier property is one or moreselected from the group consisting of water resistance, lipidresistance, and gas resistance.
 13. A barrier formulation, comprising:the enhanced cellulose nanofibril binder according to claim 1; a secondSGF blend, the second SGF blend comprising one or more selected from thegroup consisting of saccharide fatty acid esters (SFAE), glycerides, andfatty acid salts; and water.
 14. (canceled)
 15. A method for imparting abarrier property to a cellulose-based material, the method comprising:contacting the cellulose-based material with a barrier formulationaccording to claim 1; and binding the barrier formulation to a surfaceof the cellulose-based material to obtain a bound cellulose-basedmaterial having the barrier property, wherein the barrier property isone or more selected from the group consisting of water resistance,lipid resistance, and gas resistance.
 16. (canceled)
 17. (canceled) 18.(canceled)
 19. (canceled)
 20. (canceled)
 21. (canceled)
 22. (canceled)23. (canceled)
 24. (canceled)
 25. (canceled)
 26. (canceled) 27.(canceled)
 28. A method of making an enhanced cellulose nanofibrilbinder, the method comprising: obtaining an aqueous mixture of cellulosenanofibrils (CNF); obtaining an aqueous SGF blend, the aqueous SGF blendcomprising one or more selected from the group consisting of saccharidefatty acid esters (SFAE), glycerides, fatty acid salts, natural waxes,and cellulose crosslinkers; and mixing the aqueous mixture of CNF withthe aqueous SGF blend to obtain a CNF/SGF mixture and allowing the CNFto bind to the SGF blend to obtain the enhanced cellulose nanofibrilbinder.
 29. (canceled)
 30. A method of making an enhanced cellulosenanofibril binder, the method comprising: obtaining an aqueous mixtureof cellulose pulp; obtaining an aqueous SGF blend, the aqueous SGF blendcomprising one or more selected from the group consisting of saccharidefatty acid esters (SFAE), glycerides, fatty acid salts, natural waxes,and cellulose crosslinkers; mixing the aqueous mixture of cellulose pulpwith the aqueous SGF blend to obtain a cellulose/SGF mixture; andsubjecting the cellulose/SGF mixture to mechanical shear forces toobtain the enhanced cellulose nanofibril binder.
 31. (canceled)
 32. Amethod of making a molded article, the method comprising: providing aforming tool having a three-dimensional shape comprising a formingportion, bringing the forming portion into contact with a cellulosecomposition so that the forming portion is covered with a wet layer ofpulp; and dewatering the layer of pulp on the forming tool to achievethe molded article, wherein the cellulose composition comprisescellulose pulp and the enhanced cellulose nanofibril binder according toclaim
 1. 33. (canceled)
 34. (canceled)
 35. (canceled)
 36. (canceled) 37.(canceled)
 38. (canceled)
 39. A method of making a molded article, themethod comprising: providing a forming tool having a three-dimensionalshape comprising a forming portion, bringing the forming portion intocontact with a cellulose composition so that the forming portion iscovered with a wet layer of pulp; and dewatering the layer of pulp onthe forming tool to achieve the molded article, wherein the cellulosecomposition comprises cellulose pulp and the barrier formulationaccording to claim
 9. 40. (canceled)
 41. A molded article obtained bythe method according to claim
 39. 42. (canceled)
 43. A method of makinga molded article, the method comprising: providing a forming tool havinga three-dimensional shape comprising a forming portion, bringing theforming portion into contact with a cellulose-based material so that theforming portion is covered with a wet layer of pulp; dewatering thelayer of pulp on the forming tool to obtain an intermediate moldedarticle; and coating a surface of the intermediate molded article withthe barrier formulation according to claim 9 by a process of immersion,spraying, painting, printing, or any combination of any of theseprocesses to achieve the molded article.
 44. (canceled)
 45. A moldedarticle obtained by the method according to claim
 43. 46. (canceled)